EP0009035B1 - selective hydrogenation of cyclopentadiene to form cyclopentene - Google Patents

selective hydrogenation of cyclopentadiene to form cyclopentene Download PDF

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Publication number
EP0009035B1
EP0009035B1 EP79930020A EP79930020A EP0009035B1 EP 0009035 B1 EP0009035 B1 EP 0009035B1 EP 79930020 A EP79930020 A EP 79930020A EP 79930020 A EP79930020 A EP 79930020A EP 0009035 B1 EP0009035 B1 EP 0009035B1
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EP
European Patent Office
Prior art keywords
alkyl
compound
carbon atoms
hydrogen
cyclopentadiene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP79930020A
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German (de)
English (en)
French (fr)
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EP0009035A1 (en
Inventor
Henry Robert Menapace
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Goodyear Tire and Rubber Co
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Goodyear Tire and Rubber Co
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Publication of EP0009035A1 publication Critical patent/EP0009035A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B01J31/0238—Amines with a primary amino group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0214—Aryloxylates, e.g. phenolates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C07C5/05—Partial hydrogenation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated

Definitions

  • This invention is directed to the selective hydrogenation of dienes to monoolefins, particularly to the selective hydrogenation of cyclopentadiene to cyclopentene. More specifically, it is directed to a process wherein cyclopentene is prepared which comprises selectively hydrogenating cyclopentadiene in a liquid phase by contacting cyclopentadiene with hydrogen in the presence of a hydrogenation catalyst comprising (1) a soluble nickel compound, (2) an aluminum trialkyl compound or a lithium alkyl compound, and (3) at least one cocatalyst compound selected from the group consisting of H 2 0; NH 3 ; ROH where R is an alkyl or a hydrogenated alkyl radical containing from 1 to 20 carbon atoms; where R 1 , R 2 and R 3 may be hydrogen, or an alkyl radical containing from 1 to 6 carbon atoms; where R 1 , R 2 and R 3 may be hydrogen or halogen, or an alkyl radical containing from 1 to 6 carbon atoms; R 1 OR 2 where
  • cyclopentadiene At the present time, substantial amounts of cyclopentadiene, usually as dicyclopentadiene, are available as a byproduct from the steam cracking of naphtha to produce primarily ethylene.
  • Cyclopentene has been found to be useful as a monomer for the formation of general purpose elastomers by ring opening polymerization of cyclopentene. Therefore, it is desirable to convert a portion of the excess cyclopentadiene available into a more valuable raw material, such as cyclopentene.
  • a method of selectively hydrogenating cyclopentadiene to form cyclopentene which comprises contacting cyclopentadiene with hydrogen in the presence of a catalyst which is a mixture of a nickel alkyl compound, such as nickel salts of carboxylic acids, nickel acetylacetonate, nickel salicaldehyde, bis(salicaldehyde), nickel, ethylene diamine, nickel, bis(x-furyl dioxime)nickel, and nickel tetracarbonyl.
  • a nickel alkyl compound such as nickel salts of carboxylic acids, nickel acetylacetonate, nickel salicaldehyde, bis(salicaldehyde), nickel, ethylene diamine, nickel, bis(x-furyl dioxime)nickel, and nickel tetracarbonyl.
  • the process of the present invention differs from all of this prior art in that it employs a third cocatalyst in certain amounts relative to the aluminium and nickel compound.
  • the cyclopentadiene employed in the formation of cyclopentene by hydrogenation is usually obtained by depolymerizing or cracking dicyclopentadiene.
  • the depolymerization of dicyclopentadiene is accomplished by heating the dimer at a temperature above 150°C. under atmospheric pressure in a conventional cracking apparatus.
  • the depolymerized material should be hydrogenated without substantial delay because it is also known that redimerization will occur upon standing.
  • cyclopentadiene can be selectively hydrogenated to cyclopentene, in the liquid phase by contacting cyclopentadiene with hydrogen in the presence of a catalyst comprising
  • the temperature at which the cyclopentadiene may be hydrogenated in accordance with the present invention may range from about 0°C. to about 250°C. with about 20 to about 100°C. being more preferred and 30 to 80°C. being most preferred.
  • inert, aromatic and aliphatic solvents may be employed as the reaction medium. Almost any aromatic or aliphatic hydrocarbon may be employed so long as the catalyst components are soluble in said solvent and the cyclopentadiene reactant is, likewise, soluble in said solvent.
  • aliphatic solvents are heptane, octane, cyclopentane and the like.
  • Typical examples of such inert aromatic solvents are benzene, toluene, xylene, and the like.
  • the molar ratio of the catalyst components employed in the process of this invention may vary widely.
  • the molar ratio of the particular cocatalyst compound to the soluble nickel compound may vary from about 1/1 to about 4/1 with a molar ratio of cocatalyst compound/Ni from 1.5/1 to 3/1 being more preferred.
  • the molar ratio of the organoaluminum compound or the lithium alkyl compound to the soluble nickel compound (Al/Ni) (Li/Ni) may vary from about 6/1 to about 12/1, with about 7/1 to 9/1 being preferred.
  • the amount of catalyst to the cyclopentadiene hydrogenated has not been found to be critical and may vary widely from a cyclopentadiene/nickel molar ratio of about 100/1 to about 20,000/1 and has been proved to be satisfactory in the performance of the invention. On the other hand, better reaction rates and more economical operating conditions would be to employ a cyclopentadiene/Ni mole ratio of from 5000/1 to about 15,000/1.
  • the first catalyst component of the catalyst system of this invention is a soluble nickel compound.
  • soluble is meant soluble in inert solvents.
  • organonickel compounds are nickel benzoate, nickel acetate, nickel naphthenate, nickel octanoate, bis(a-furyl dioxime) nickel, nickel palmitate, nickel stearate, nickel acetylacetonate, nickel salicaldehyde, bis(cyclopentadiene) nickel, bis(salicylaldehyde)ethylene diimine nickel, cyclo-pentadienyl-nickel, nitrosyl, bis(n-allyl nickel trifluoroacetate), and nickel tetracarbonyl.
  • the preferred component containing nickel is a nickel salt of a carboxylic acid or an organic complex compound of nickel. The most preferred are 2-ethyl hexanoate, neo-de
  • the second or (2) component is an organoaluminum compound.
  • organoaluminum compound is meant any organoaluminum compound responding to the formula: in which R, is selected from the group consisting of alkyl (including cycloalkyl), aryl, alkaryl, arylalkyl, alkoxy and hydrogen; R z and R 3 being selected from the group of alkyl (including cycloalkyl), aryl, alkaryl, and arylalkyl.
  • diethylaluminum hydride di-n-propylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenyl ethylaluminum hydride, phenyl-n-propylaluminum hydride, p-tolyl ethylaluminum hydride, p-tolyl n-propylaluminum hydride, p-tolyl isopropylaluminum hydride, benzyl ethylaluminum hydride, benzyl n-propylaluminum hydride, and benzyl isopropylaluminum hydride and other organoaluminum hydrides.
  • diethylaluminum ethoxide, diisobutylaluminum ethoxide, and dipropylaluminum methoxide are also included.
  • the second component is also a lithium alkyl compound.
  • the term lithium alkyl compound is meant to mean that the organo lithium compound corresponds to the formula R-Li in which R is a monovalent hydrocarbon radical with 1 to 20 carbon atoms, especially n-butyllithium, secondary butyllithium, hexyllithium and methyllithium are representative thereof. Of these, butyllithium is the preferred lithium compound.
  • the third catalyst (3) component has been referred to as a cocatalyst compound which may be selected from certain oxygen or nitrogen containing compounds.
  • a cocatalyst compound which may be selected from certain oxygen or nitrogen containing compounds.
  • water H 2 O
  • Anhydrous ammonia NH 3
  • ammonia in mixture with water is useful.
  • commercial ammonium hydroxide NH 4 0H
  • the third catalyst component may also be chosen from certain oxygen containing compounds such as those defined by a formula ROH wherein R is an alkyl or halogenated alkyl radical containing from 1 to 20 carbon atoms.
  • ROH an alkyl or halogenated alkyl radical containing from 1 to 20 carbon atoms.
  • Representative examples of this class of compounds are the simple alcohols such as methanol, ethanol, butanol, hexanol, chloroethanol and the like.
  • the third catalyst component may also be chosen from those compounds represented by the formula wherein R ' , R 2 and R 3 may be hydrogen or an alkyl radical containing from 1 to 6 carbon atoms.
  • Representative examples of the cocatalysts responding to this formula are phenol, 4-methyl phenol, 3-methyl phenol, 4-butyl phenol and the like.
  • the third catalyst component may also be represented by the compounds responding to the formula wherein R 1 , R 2 and R 3 may be hydrogen, halogen or an alkyl radical containing from 1 to 6 carbon atoms.
  • Representative examples of such materials responding to this formula are aniline, 2-methyl aniline, 4-methyl aniline, 3-chloroaniline, 4-butyl aniline, 3,4-dimethylaniline, 3,4-dichloroaniline and the like.
  • R,-O-R z Another class of compounds which may be employed as cocatalysts in the practice of this invention are those ethers represented by the formula R,-O-R z wherein R, and R z may be the same or different alkyl radicals containing from 1 to 6 carbon atoms. Representative examples of such compounds would be methyl ethyl ether, diethyl ether, dimethyl ether, dibutyl ether and the like.
  • Still another class of cocatalysts which may be employed in this invention are the compounds responding to the formula wherein R i may be an alkyl or aromatic radical of from 1 to 8 carbon atoms and R 2 may be hydrogen or an alkyl or aromatic radical containing 1 to 8 carbon atoms.
  • R i may be an alkyl or aromatic radical of from 1 to 8 carbon atoms
  • R 2 may be hydrogen or an alkyl or aromatic radical containing 1 to 8 carbon atoms.
  • Representative of such compounds are acetaldehyde, acetone, methyl ethyl ketone, acetophenone, 3-pentanone, benzaldehyde and the like.
  • a preferred group of cocatalyst compounds are those such as water, ammonia, alcohols and phenols or mixtures thereof. Of particular interest are mixtures of water and ammonia.
  • the catalyst components employed in the hydrogenation catalyst of the invention are soluble in the cyclopentadiene reactant and are soluble in the cyclopentene product.
  • the reactant cyclopentadiene and the product cyclopentene and the catalyst used in this invention are also soluble in a variety of inert solvents, either aromatic or aliphatic, such as pentane, cyclopentane, n-octane, toluene, benzene and the like.
  • a solvent may be used. If a solvent is used, the cyclopentadiene/solvent volume ratio may vary from 1/1 to 200/1.
  • a series of different catalysts were prepared in which a typical procedure using 1.30 millimoles (mmol) of the particular cocatalyst compound were added to 0.65 mmol of nickel octanoate as a 0.1 molar solution in toluene to a series of dry 4-oz bottles under nitrogen. After mixing the cocatalyst and the nickel octanoate for 5 minutes at room temperature, 4.55 mmol of triethylaluminum as a 2 molar solution in toluene were added under nitrogen and the mixture stirred for at least two additional minutes.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
EP79930020A 1978-08-30 1979-08-27 selective hydrogenation of cyclopentadiene to form cyclopentene Expired EP0009035B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/938,159 US4204081A (en) 1978-08-30 1978-08-30 Selective hydrogenation of cyclopentadiene to form cyclopentene
US938159 2001-08-23

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EP0009035A1 EP0009035A1 (en) 1980-03-19
EP0009035B1 true EP0009035B1 (en) 1983-03-09

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EP79930020A Expired EP0009035B1 (en) 1978-08-30 1979-08-27 selective hydrogenation of cyclopentadiene to form cyclopentene

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US (1) US4204081A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (1) EP0009035B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS5535083A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BR (1) BR7905424A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (1) CA1115735A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2964993D1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
ZA (1) ZA794016B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Families Citing this family (9)

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Publication number Priority date Publication date Assignee Title
US4570025A (en) * 1985-06-14 1986-02-11 Phillips Petroleum Company Preparation of alkenes and cycloalkenes
JP2718059B2 (ja) * 1988-04-28 1998-02-25 日本合成ゴム株式会社 重合体の水素添加方法および触媒
JPH0236223A (ja) * 1988-07-27 1990-02-06 Nippon Oil Co Ltd 淡色な樹脂の製造方法
JP2969771B2 (ja) * 1989-12-22 1999-11-02 ジェイエスアール株式会社 オレフィン性不飽和重合体の水素添加方法および水素添加用触媒組成物
FR2736562B1 (fr) * 1995-07-11 1997-09-19 Inst Francais Du Petrole Nouvelle composition catalytique pour catalyse biphasique, en particulier a base de complexes du nickel et procede pour l'oligomerisation des olefines
CN111085268B (zh) * 2018-10-24 2023-07-21 中国石油化工股份有限公司 聚苯乙烯加氢制聚环己烷基乙烯的加氢催化剂及制备方法和加氢方法
CN111085269B (zh) * 2018-10-24 2023-03-14 中国石油化工股份有限公司 环戊二烯加氢制环戊烯加氢催化剂及其制备方法和加氢方法
CN111085272B (zh) * 2018-10-24 2023-05-12 中国石油化工股份有限公司 聚苯乙烯加氢制聚环己烷基乙烯的加氢催化剂及制备方法和加氢方法
CN111085271B (zh) * 2018-10-24 2023-04-11 中国石油化工股份有限公司 制备氢化苯乙烯-共轭二烯共聚物的加氢催化剂及制备方法、加氢方法和氢化共聚物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3022359A (en) * 1959-04-07 1962-02-20 Exxon Research Engineering Co Selective hydrogenation of cyclododecatriene to cyclododecene
GB1046780A (en) * 1963-04-18 1966-10-26 Geigy Co Ltd Improvements in or relating to selective hydrogenation
GB1369676A (en) * 1971-02-19 1974-10-09 Int Synthetic Rubber Cyclopentene preparation
US3937745A (en) * 1974-08-29 1976-02-10 The Goodyear Tire & Rubber Company Selective hydrogenation of cyclopentadiene
IT1038403B (it) * 1975-05-23 1979-11-20 Snam Progetti Procedimento di idrogenazione selettiva in fase gassosa di composti plurinsaturi

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ZA794016B (en) 1980-11-26
JPS5535083A (en) 1980-03-11
EP0009035A1 (en) 1980-03-19
US4204081A (en) 1980-05-20
DE2964993D1 (en) 1983-04-14
CA1115735A (en) 1982-01-05
JPS621374B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1987-01-13
BR7905424A (pt) 1980-05-20

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